Hard surface cleaning composition having a malodor control component and methods of cleaning hard surfaces

ABSTRACT

A hard surface cleaning composition comprising a malodor control component, and methods of cleaning hard surfaces are provided. In some embodiments, the hard surface cleaning composition comprises at least one volatile aldehyde and an acid catalyst.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional Application No.61/287,348, filed Dec. 17, 2009 and U.S. Provisional Application No.61/287,369, filed Dec. 17, 2009 and U.S. Provisional No. 61/287,383,filed Dec. 17, 2009.

FIELD OF THE INVENTION

The present invention relates to hard surface cleaning compositionshaving a malodor control component, and methods for cleaning hardsurfaces.

BACKGROUND OF THE INVENTION

Scented hard surface cleaning compositions are known. Typically, hardsurface cleaning manufacturers develop perfume technology that providesa pleasant scent and masks malodors associated with soiled hardsurfaces.

However, not all odors on hard surfaces are effectively controlled byproducts on the market because amine-based malodors such as fish andurine malodors, and sulfur-based malodors such as garlic, onion, foot,and fecal malodors are difficult to combat. Further, the time requiredfor a product to noticeably combat malodors may create consumer doubt asto a product's efficacy on malodors. For example, the consumer mayfinish cleaning a hard surface and leave the area before the productbegins to noticeably reduce the malodor.

The difficulty in overcoming a broad range of malodors has spawned adiverse assortment of products to neutralize, mask, or contain themalodors. There remains a need for a hard surface cleaning compositionthat cleans and is effective on a broad range of malodors, includingamine-based and sulfur-based malodors, while not overpowering malodorswith an overwhelming perfume.

SUMMARY OF THE INVENTION

In one embodiment, there is provided a hard surface cleaning compositioncomprising: (a) an acidic component; (b) a surfactant selected from thegroup consisting of nonionic surfactants, anionic surfactants, cationicsurfactants; amphoteric surfactants, zwitterionic surfactants, andmixtures thereof; and (c) a surface modifying polymer; (d) a malodorcontrol component comprising an effective amount of two or more volatilealdehydes for neutralizing a malodor, wherein said two or more volatilealdehydes are selected from the group consisting of 2-ethoxybenzylaldehyde, 2-isopropyl-5-methyl-2-hexenal, 5-methyl furfural,5-methyl-thiophene-carboxaldehyde, adoxal, p-anisaldehyde,benzylaldehyde, bourgenal, cinnamic aldehyde, cymal, decyl aldehyde,floral super, florhydral, helional, lauric aldehyde, ligustral, lyral,melonal, o-anisaldehyde, pino acetaldehyde, P.T. bucinal, thiophenecarboxaldehyde, trans-4-decenal, trans trans 2,4-nonadienal, undecylaldehyde, and mixtures thereof; and (e) an aqueous carrier.

In another embodiment, there is provided a hard surface cleaningcomposition comprising: (a) an acidic mixture comprising formic acid andcitric acid; (b) a surface modifying polymer selected from the groupconsisting of: vinylpyrrolidone homopolymer or copolymer; polysaccharidepolymer, and mixtures thereof; and (c) a malodor control componentcomprising: (i) at least one volatile aldehyde; and (ii) an acidcatalyst having a vapor pressure of about 0.01 to about 13 at 25° C.

In yet another embodiment, there is provided a method of cleaning a hardsurface or an object, comprising the steps of: applying the hard surfacecleaning composition of claim 1 onto said hard-surface or said object;leaving said composition on said hard-surface or said object to act;optionally, wiping said hard-surface or object; and rinsing saidhard-surface or said object.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph showing butanethiol reduction by thiophenecarboxaldehyde in combination with various acid catalysts.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a hard surface cleaning composition forcleaning a variety of hard surfaces including those found in bathrooms,garages, driveways, basements, gardens, kitchens, etc. Morespecifically, the compositions of the present invention deliver goodmalodor reduction and limescale removal performance (i.e., removal ofpure limescale deposits and/or limescale-containing soils) whilst notbeing considered corrosive. The present invention also relates tomethods of cleaning hard surfaces.

I. Hard Surface Cleaning Composition

The compositions of the present invention are liquid compositions(including gels) as opposed to a solid or a gas. The compositions of thepresent invention may have a pH of above 2.0, alternatively from 2.0 to4.0, alternatively from 2.5 to 4.0, alternatively from 3.0 to 3.9,alternatively from 3.0 to 3.6, alternatively from 2.0 to 3.6,alternatively from 2.1 to 3.6, alternatively from 2.1 to 2.9,alternatively from 2.1 to 2.4, alternatively from 2.2 to 2.4.Alternatively, the pH of the cleaning compositions herein, as ismeasured at 25° C., may be at least 2.0. The pH of the cleaningcompositions herein, as is measured at 25° C. may be less than 3.6. Inone embodiment, the compositions of the present invention are acidic andhave a pH of above 2.0.

In one embodiment, the compositions herein may have a water-likeviscosity. By “water-like viscosity” it is meant herein a viscosity thatis close to that of water. Alternatively, the liquid acidic hard surfacecleaning compositions herein have a viscosity of up to 50 cps at 60 rpm,alternatively from 0 cps to 30 cps, alternatively from 0 cps to 20 cps,alternatively from 0 cps to 10 cps at 60 rpm¹ and 20° C. when measuredwith a Brookfield digital viscometer model DV II, with spindle 2.

In another embodiment, the compositions herein are thickenedcompositions. Thus, the hard surface cleaning compositions hereinalternatively have a viscosity of from 50 cps to 5000 cps at 20 s⁻¹,alternatively from 50 cps to 2000 cps, alternatively from 50 cps to 1000cps and alternatively from 50 cps to 500 cps at 20 s⁻¹ and 20° C. whenmeasured with a Rheometer, model AR 1000 (Supplied by TA Instruments)with a 4 cm conic spindle in stainless steel, 2° angle (linear incrementfrom 0.1 to 100 sec⁻¹ in max. 8 minutes). Alternatively, the thickenedcompositions of this specific embodiment are shear-thinningcompositions. The thickened hard surface cleaning compositions hereinalternatively comprise a thickener, alternatively a polysaccharidepolymer (as described herein below) as thickener, still alternatively agum-type polysaccharide polymer thickener and alternatively Xanthan gum.

The compositions of the present invention may comprise from 70% to 99%,by weight of the total composition, of water, alternatively from 75% to95%, alternatively from 80% to 95%, and other essential and optionalcompositions components are dissolved, dispersed or suspended in water.

A. Acidic Component

The compositions of the present invention may include formic acid.Formic acid has been found to provide excellent limescale removalperformance. Formic acid is commercially available from Aldrich.

The compositions of the present invention may comprise from 0.01% to 5%,alternatively from 0.5% to 4%, alternatively from 1% to 3%, by weight ofthe total composition of formic acid.

The compositions of the present invention may comprise citric acid.Suitable citric acid is commercially available from Aldrich, ICI orBASF.

The compositions of the present invention may comprise from 0.1 to 12%,alternatively from 1% to 10%, alternatively from 1.5% to 8%,alternatively from 1.5% to 5% by weight of the total composition ofcitric acid.

The Applicant has unexpectedly found that by using a formic acid andcitric acid-containing composition having a pH of above 2.0, the acidiccomposition provides good cleaning performance whilst not beingcorrosive. Indeed, a similar composition having a pH below 2.0 (i.e.,un-buffered or not sufficiently buffered) will be corrosive. Indeed, thecombination of acids along with the selected pH provides an optimalcombination of limescale removal and non-corrosiveness is achieved.

By “corrosive” it is meant herein that the composition has to be labeledas corrosive by means of appropriate text and/or pictograms under theDirective 1999/45/EC of the European Parliament and of the Council of 31May 1999 concerning the approximation of the laws, regulations andadministrative provisions of the Member States relating to theclassification, packaging and labelling of dangerous preparations. By“non-corrosive” or “not being/considered corrosive” or the like it ismeant herein that the composition has not to be labeled as corrosive bymeans of appropriate text and/or pictograms under the above Directive.

Indeed, it has been found that hard surface cleaning compositionscomprising formic acid and citric acid and having a pH of above 2.0(alternatively 2.01-3.6), provide a similar or even improved limescaleremoval performance (i.e., limescale deposits cleaning performance andlimescale-containing soil cleaning performance), as compared to thelimescale removal performance obtained by a similar composition having asimilar pH as claimed herein but comprising formic acid or citric acidon their own or other compositions having a lower pH as claimed hereinand comprising formic acid or citric acid in combination with anotheracid (such as sulfuric acid), at comparable levels of free-acidity.

Furthermore, hard surface cleaning compositions having a pH of above 2.0and comprising formic acid and citric acid as claimed herein, are notconsidered corrosive.

The present invention also encompasses the use, in a liquid acidic hardsurface cleaning composition, of formic acid, citric acid and analkaline material, at a pH of above 2.0, to provide limescale removalperformance, whilst not being corrosive.

The composition of the present invention may also include other acids,alternatively acetic acid and/or oxalic acid and/or lactic acid.

It has been found that the presence of lactic acid additionally providesantimicrobial/disinfecting benefits to the compositions of the presentinvention. Lactic acid is commercially available from Aldrich or Purac.

The compositions of the present invention may comprise from 0.1 to 1%,alternatively from 0.1% to 0.75% by weight of the composition of lacticacid.

The compositions herein may comprise acetic acid. Suitable acetic acidis commercially available from Aldrich, ICI or BASF.

The compositions of the present invention may comprise from 0.1 to 1%,alternatively from 0.1% to 0.75% by weight of the composition of aceticacid.

The compositions herein may comprise oxalic acid. Suitable oxalic acidis commercially available from Aldrich or Clariant.

The compositions of the present invention may comprise from 0.1 to 1%,alternatively from 0.1% to 0.75% by weight of the composition of oxalicacid.

B. Alkaline Component

The compositions herein comprise an alkaline material. Indeed, analkaline material may be present to trim the pH and/or maintain the pHof the compositions of the present invention. Examples of alkalinematerial are sodium hydroxide, potassium hydroxide and/or lithiumhydroxide, and/or the alkali metal oxides such, as sodium and/orpotassium oxide or mixtures thereof and/or monoethanolamine and/ortriethanolamine. Other suitable bases include ammonia, ammoniumcarbonate, choline base, etc. In one embodiment, the source ofalkalinity is sodium hydroxide or potassium hydroxide, alternativelysodium hydroxide.

Typically the amount of alkaline material is of from 0.001% to 20%,alternatively from 0.01% to 10% and alternatively from 0.05% to 3%, byweight of the composition.

Despite the presence of alkaline material, if any, the compositionsherein may remain acidic compositions.

C. Chelating Agent

The compositions of the present invention may comprise a chelating agentor mixtures thereof. Chelating agents can be incorporated in thecompositions herein in amounts ranging from 0% to 10% by weight of thetotal composition, alternatively 0.01% to 5.0%, alternatively 0.05% to1%.

Suitable phosphonate chelating agents to be used herein may includealkali metal ethane 1-hydroxy diphosphonates (HEDP), alkylenepoly(alkylene phosphonate), as well as amino phosphonate compounds,including amino aminotri(methylene phosphonic acid) (ATMP), nitrilotrimethylene phosphonates (NTP), ethylene diamine tetra methylenephosphonates, and diethylene triamine penta methylene phosphonates(DTPMP). The phosphonate compounds may be present either in their acidform or as salts of different cations on some or all of their acidfunctionalities.

Suitable chelating agents to be used herein are diethylene triaminepenta methylene phosphonate (DTPMP) and ethane 1-hydroxy diphosphonate(HEDP). In one execution of the present invention, the chelating agentis selected to be ethane 1-hydroxy diphosphonate (HEDP). Suchphosphonate chelating agents are commercially available from Monsantounder the trade name DEQUEST®.

Polyfunctionally-substituted aromatic chelating agents may also beuseful in the compositions herein. See U.S. Pat. No. 3,812,044, issuedMay 21, 1974, to Connor et al. Suitable compounds of this type in acidform are dihydroxydisulfobenzenes such as1,2-dihydroxy-3,5-disulfobenzene.

One biodegradable chelating agent for use herein is ethylene diamineN,N′-disuccinic acid, or alkali metal, or alkaline earth, ammonium orsubstitutes ammonium salts thereof or mixtures thereof. EthylenediamineN,N′-disuccinic acids, especially the (S,S) isomer have been extensivelydescribed in U.S. Pat. No. 4,704,233, Nov. 3, 1987, to Hartman andPerkins. Ethylenediamine N,N′-disuccinic acids is, for instance,commercially available under the tradename ssEDDS® from Palmer ResearchLaboratories.

Suitable amino carboxylates to be used herein include ethylene diaminetetra acetates, diethylene triamine pentaacetates, diethylene triaminepentaacetate (DTPA), N-hydroxyethylethylenediamine triacetates,nitrilotri-acetates, ethylenediamine tetrapropionates,triethylenetetraaminehexa-acetates, ethanol-diglycines, propylenediamine tetracetic acid (PDTA) and methyl glycine di-acetic acid (MGDA),both in their acid form, or in their alkali metal, ammonium, andsubstituted ammonium salt forms. Particularly suitable aminocarboxylates to be used herein are diethylene triamine penta aceticacid, propylene diamine tetracetic acid (PDTA) which is, for instance,commercially available from BASF under the trade name Trilon FS® andmethyl glycine di-acetic acid (MGDA).

Further carboxylate chelating agents to be used herein include salicylicacid, aspartic acid, glutamic acid, glycine, malonic acid or mixturesthereof.

It has been surprisingly found that the addition of a chelating agent,alternatively HEDP, in the composition of the present invention providesan unexpected improvement in terms of limescale removal.

D. Surfactants

The compositions of the present invention may comprise a nonionicsurfactant, or a mixture thereof and/or an anionic surfactant or amixture thereof. In one embodiment, the compositions of the presentinvention, comprise a mixture of a nonionic surfactant or a mixturethereof and an anionic surfactant or a mixture thereof. Indeed, it hasbeen surprisingly found that such a mixture contributes to the limescaleand greasy soap scum removal performance of the compositions herein.

The compositions of the present invention may comprise a nonionicsurfactant, or a mixture thereof. This class of surfactants may bedesired as it further contributes to cleaning performance of the hardsurface cleaning compositions herein. It has been found in particularthat nonionic surfactants strongly contribute in achieving highlyimproved performance on greasy soap scum removal, the benefit isespecially observed at a pH above 3.0.

The compositions of the present invention may comprise up to 15% byweight of the total composition of a nonionic surfactant or a mixturethereof, alternatively from 0.1% to 15%, alternatively from 1% to 10%,even alternatively from 1% to 5%, and alternatively from 1% to 3%.

Suitable nonionic surfactants for use herein are alkoxylated alcoholnonionic surfactants, which can be readily made by condensationprocesses which are well-known in the art. However, a great variety ofsuch alkoxylated alcohols, especially ethoxylated and/or propoxylatedalcohols, is conveniently commercially available. Surfactants catalogsare available which list a number of surfactants, including nonionics.

Accordingly, suitable alkoxylated alcohols for use herein are nonionicsurfactants of the formula RO(E)e(P)pH where R is a hydrocarbon chain offrom 2 to 24 carbon atoms, E is ethylene oxide and P is propylene oxide,and e and p which represent the average degree of, respectivelyethoxylation and propoxylation, are of from 0 to 24 (with the sum of e+pbeing at least 1). Alternatively, the hydrophobic moiety of the nonioniccompound can be a primary or secondary, straight or branched alcoholhaving from 8 to 24 carbon atoms.

Suitable nonionic surfactants for use in the compositions of theinvention are the condensation products of ethylene oxide and/orpropylene oxide with alcohols having a straight or branched alkyl chain,having from 6 to 22 carbon atoms, wherein the degree of alkoxylation(ethoxylation and/or propoxylation) is from 1 to 15, alternatively from5 to 12. Such suitable nonionic surfactants are commercially availablefrom Shell, for instance, under the trade name Neodol® or from BASFunder the trade name Lutensol®.

The compositions of the present invention may comprise an anionicsurfactant or a mixture thereof. The compositions of the presentinvention may comprise up to 15% by weight of the total composition ofan anionic surfactant or a mixture thereof, alternatively from 0.1% to15%, alternatively from 1% to 10%, even alternatively from 1% to 5%, andalternatively from 1% to 3%.

Anionic surfactants may be included herein as they contribute to thecleaning benefits of the hard-surface cleaning compositions of thepresent invention. Indeed, the presence of an anionic surfactantcontributes to the greasy soap scum cleaning of the compositions herein.More generally, the presence of an anionic surfactant in the liquidacidic compositions of the present invention allows to lower the surfacetension and to improve the wettability of the surfaces being treatedwith the liquid acidic compositions of the present invention.Furthermore, the anionic surfactant or a mixture thereof, helps tosolubilize the soils in the compositions of the present invention.

Suitable anionic surfactants for use herein are all those commonly knownby those skilled in the art. In one embodiment, the anionic surfactantsfor use herein include alkyl sulphonates, alkyl aryl sulphonates, ormixtures thereof.

Suitable linear alkyl sulphonates include C8 sulphonate like Witconate®NAS 8 commercially available from Witco.

Other anionic surfactants useful herein include salts (including, forexample, sodium, potassium, ammonium, and substituted ammonium saltssuch as mono-, di- and triethanolamine salts) of soap, alkyl sulphates,alkyl aryl sulphates alkyl alkoxylated sulphates, C8-C24olefinsulfonates, sulphonated polycarboxylic acids prepared bysulphonation of the pyrolyzed product of alkaline earth metal citrates,e.g., as described in British patent specification No. 1,082,179; alkylester sulfonates such as C14-16 methyl ester sulfonates; acyl glycerolsulfonates, alkyl phosphates, isethionates such as the acylisethionates, N-acyl taurates, alkyl succinamates, acyl sarcosinates,sulfates of alkylpolysaccharides such as the sulfates ofalkylpolyglucoside (the nonionic nonsulfated compounds being describedbelow), alkyl polyethoxy carboxylates such as those of the formulaRO(CH2CH2O)kCH2COO-M+ wherein R is a C8-C22 alkyl, k is an integer from0 to 10, and M is a soluble salt-forming cation. Resin acids andhydrogenated resin acids are also suitable, such as rosin, hydrogenatedrosin, and resin acids and hydrogenated resin acids present in orderived from tall oil. Further examples are given in “Surface ActiveAgents and Detergents” (Vol. I and II by Schwartz, Perry and Berch). Avariety of such surfactants are also generally disclosed in U.S. Pat.No. 3,929,678, issued Dec. 30, 1975 to Laughlin, et al. at Column 23,line 58 through Column 29, line 23.

E. Surface-Modifying Polymer

The compositions of the present invention may optionally comprise avinylpyrrolidone homopolymer or copolymer, or a mixture thereof.Typically, the compositions of the present invention may comprise from0.01% to 5% by weight of the total composition, of a vinylpyrrolidonehomopolymer or copolymer, or a mixture thereof, alternatively from 0.05%to 3%, alternatively from 0.05% to 1%.

Suitable vinylpyrrolidone homopolymers for use herein are homopolymersof N-vinylpyrrolidone having the following repeating monomer:

wherein n (degree of polymerisation) is an integer of from 10 to1,000,000, alternatively from 20 to 100,000, and alternatively from 20to 10,000.

Accordingly, suitable vinylpyrrolidone homopolymers (“PVP”) for useherein have an average molecular weight of from 1,000 to 100,000,000,alternatively from 2,000 to 10,000,000, alternatively from 5,000 to1,000,000, and alternatively from 50,000 to 500,000.

Suitable vinylpyrrolidone homopolymers are commercially available fromISP Corporation, New York, N.Y. and Montreal, Canada under the productnames PVP K-15® (viscosity molecular weight of 10,000), PVP K-30®(average molecular weight of 40,000), PVP K-60® (average molecularweight of 160,000), and PVP K-90® (average molecular weight of 360,000).Other suitable vinylpyrrolidone homopolymers which are commerciallyavailable from BASF Cooperation include Sokalan HP 165®, Sokalan HP 12®,Luviskol K30®, Luviskol K60®, Luviskol K80®, Luviskol K90®;vinylpyrrolidone homopolymers known to persons skilled in the detergentfield (see for example EP-A-262,897 and EP-A-256,696).

Suitable copolymers of vinylpyrrolidone for use herein includecopolymers of N-vinylpyrrolidone and alkylenically unsaturated monomersor mixtures thereof.

The alkylenically unsaturated monomers of the copolymers herein includeunsaturated dicarboxylic acids such as maleic acid, chloromaleic acid,fumaric acid, itaconic acid, citraconic acid, phenylmaleic acid,aconitic acid, acrylic acid, N-vinylimidazole and vinyl acetate. Any ofthe anhydrides of the unsaturated acids may be employed, for exampleacrylate, methacrylate. Aromatic monomers like styrene, sulphonatedstyrene, alpha-methyl styrene, vinyl toluene, t-butyl styrene andsimilar well known monomers may be used.

For example, suitable N-vinylimidazole N-vinylpyrrolidone polymers foruse herein have an average molecular weight range from 5,000 to1,000,000, alternatively from 5,000 to 500,000, alternatively from10,000 to 200,000. The average molecular weight range was determined bylight scattering as described in Barth H. G. and Mays J. W. ChemicalAnalysis Vol 113, “Modern Methods of Polymer Characterization”.

Such copolymers of N-vinylpyrrolidone and alkylenically unsaturatedmonomers like PVP/vinyl acetate copolymers are commercially availableunder the trade name Luviskol® series from BASF.

In one execution of the present invention, vinylpyrrolidone homopolymersare selected.

The compositions of the present invention may optionally comprise apolysaccharide polymer or a mixture thereof. Typically, the compositionsof the present invention may comprise from 0.01% to 5%, by weight of thetotal composition, of a polysaccharide polymer or a mixture thereof,alternatively from 0.05% to 3%, alternatively from 0.05% to 1%.

Suitable polysaccharide polymers for use herein include substitutedcellulose materials like carboxymethylcellulose, ethyl cellulose,hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxymethylcellulose, succinoglycan and naturally occurring polysaccharide polymerslike Xanthan gum, gellan gum, guar gum, locust bean gum, tragacanth gumor derivatives thereof, or mixtures thereof.

In one embodiment, the compositions of the present invention comprise apolysaccharide polymer selected from the group consisting of:carboxymethylcellulose, ethyl cellulose, hydroxyethyl cellulose,hydroxypropyl cellulose, hydroxymethyl cellulose, succinoglycan gum,Xanthan gum, gellan gum, guar gum, locust bean gum, tragacanth gum,derivatives of the aforementioned, and mixtures thereof. Alternatively,the compositions herein comprise a polysaccharide polymer selected fromthe group consisting of: succinoglycan gum, Xanthan gum, gellan gum,guar gum, locust bean gum, tragacanth gum, derivatives of theaforementioned, and mixtures thereof. Alternatively, the compositionsherein comprise a polysaccharide polymer selected from the groupconsisting of: Xanthan gum, gellan gum, guar gum, derivatives of theaforementioned, and mixtures thereof. Alternatively, the compositionsherein comprise Xanthan gum, derivatives thereof, or mixtures thereof.

Particularly polysaccharide polymers for use herein are Xanthan gum andderivatives thereof. Xanthan gum and derivatives thereof may becommercially available for instance from CP Kelco under the trade nameKeltrol RD®, Kelzan S® or Kelzan T®. Other suitable Xanthan gums arecommercially available by Rhodia under the trade name Rhodopol T® andRhodigel X747®. Succinoglycan gum for use herein is commerciallyavailable by Rhodia under the trade name Rheozan®.

It has surprisingly been found that the polysaccharide polymers ormixtures thereof herein act as surface modifying polymers (alternativelycombined with a vinylpyrrolidone homopolymer or copolymer, as describedherein) and/or as thickening agents. Indeed, the polysaccharide polymersor mixtures thereof herein can be used to thicken the compositions ofthe present invention. It has been surprisingly found that the use ofpolysaccharide polymers or mixtures thereof herein, and alternativelyXanthan gum, provides excellent thickening performance to thecompositions herein. Moreover, it has been found that the use ofpolysaccharide polymers or mixtures thereof herein, and alternativelyXanthan gum, provides excellent thickening whilst not or only marginallyreducing the limescale removal performance. Indeed, thickenedcompositions usually tend to show a drop in soil/stain removalperformance (which in turn requires an increased level of actives tocompensate for the performance drop) due to the thickening. It has beenfound that this is due to the fact that the actives providing thesoil/stain removal performance are less free to migrate to thesoil/stain. However, it has been surprisingly found that whenpolysaccharide polymers or mixtures thereof herein, and alternativelyXanthan gum, are used as thickeners for the compositions herein, thedrop in soil/stain removal performance is substantially reduced or evenprevented.

Furthermore, without intending to be bound by theory, it has been shownthat vinylpyrrolidone homopolymers or copolymers, alternatively thevinylpyrrolidone homopolymer, and polysaccharide polymers, alternativelyXanthan gum or derivatives thereof, described herein, when added into anaqueous acidic composition deliver improved shine to the treated surfaceas well as improved next-time cleaning benefit on said surface, whiledelivering good first-time hard-surface cleaning performance and goodlimescale removal performance. Furthermore, the formation of watermarksand/or limescale deposits upon drying is reduced or even eliminated.

Moreover, the vinylpyrrolidone homopolymers or copolymers andpolysaccharide polymers further provide long lasting protection againstformation of watermarks and/or deposition of limescale deposits, hence,long lasting shiny surfaces.

An additional advantage related to the use of the vinylpyrrolidonehomopolymers or copolymers and polysaccharide polymers, in the acidiccompositions herein, is that as they adhere on hard surface making themmore hydrophilic, the surfaces themselves become smoother (this can beperceived by touching said surfaces) and this contributes to conveyperception of surface perfectly descaled.

These benefits may be obtained at low levels of vinylpyrrolidonehomopolymers or copolymers and polysaccharide polymers, alternativelyXanthan gum or derivatives thereof, described herein.

The compositions herein may further comprise a surface-modifying polymerother than the vinylpyrrolidone homo- or copolymers and polysaccharidepolymers described herein above.

The composition herein may comprise up to 5%, alternatively of from0.0001% to 3%, alternatively from 0.001% to 2%, and alternatively offrom 0.01% to 1%, by weight of the total composition of said othersurface-modifying polymers.

Other surface-modifying polymers may be optional ingredients herein asthey deposit onto the surfaces cleaned with a composition of the presentinvention. Thereby, soil adherence, soap scum, limescale and/or mineralencrustation build-up, is prevented.

Suitable other surface-modifying polymers may be selected from the groupconsisting of: zwitterionic surface modification copolymers consistingof carboxylate- and permanent cationic-moieties; zwitterionic surfacemodifying polysulphobetaine copolymers; zwitterionic surface modifyingpolybetaine copolymers; silicone glycol polymers; and mixtures thereof.

Zwitterionic surface modification copolymers consisting of carboxylate-and permanent cationic-moieties, zwitterionic surface modifyingpolysulphobetaine copolymers and zwitterionic surface modifyingpolybetaine copolymers are described in WO 2004/083354, EP-A-1196523 andEP-A-1196527. Suitable zwitterionic surface modification copolymersconsisting of carboxylate- and permanent cationic-moieties, zwitterionicsurface modifying polysulphobetaine copolymers and zwitterionic surfacemodifying polybetaine copolymers are commercially available from Rhodiain the Mirapol SURF S-polymer series.

Alternative surface modification copolymers are described in theApplicant's co-pending European Patent Applications 07 113 156.9, thesecopolymers are sulphobetaine/vinyl-pyrrolidone and its derivativescopolymers. A particularly suitable sulphobetaine/vinyl-pyrrolidone andits derivatives copolymer is a copolymer of 90% moles of vinylpyrrolidone and 10% moles of SPE (sulphopropyl dimethyl ammonium ethylmethacrylate) such as exemplified in Example 1.1 of the Applicant'sco-pending European Patent Applications 07 113 156.9.

Suitable silicone glycols are described in the Applicant's co-pendingEuropean Patent Applications 03 447 099.7 and 03 447 098.9, in thesection titled “Silicone glycol”.

Silicone glycol polymers are commercially available from Generalelectric, Dow Corning, and Witco (see European Patent Applications 03447 099.7 and 03 447 098.9 for an extensive list of trade names ofsilicone glycol polymers).

In one embodiment of the present invention, the silicone glycol polymerherein is a Silicones-Polyethers copolymer, commercially available underthe trade name SF 1288® from Momentive Performance Materials.

F. Radical Scavenger

The compositions of the present invention may further comprise a radicalscavenger or a mixture thereof.

Suitable radical scavengers for use herein include the well-knownsubstituted mono and dihydroxy benzenes and their analogs, alkyl andaryl carboxylates and mixtures thereof. Radical scavengers for useherein may include di-tert-butyl hydroxy toluene (BHT), hydroquinone,di-tert-butyl hydroquinone, mono-tert-butyl hydroquinone,tert-butyl-hydroxy anysole, benzoic acid, toluic acid, catechol, t-butylcatechol, benzylamine,1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, n-propyl-gallateor mixtures thereof, and di-tert-butyl hydroxy toluene. Such radicalscavengers like N-propyl-gallate may be commercially available from NipaLaboratories under the trade name Nipanox S1®.

Radical scavengers, when used, may be typically present herein inamounts up to 10% by weight of the total composition and alternativelyfrom 0.001% to 0.5% by weight. The presence of radical scavengers maycontribute to the chemical stability of the compositions of the presentinvention.

G. Solvent

The compositions of the present invention may further comprise a solventor a mixture thereof, as an optional ingredient. Solvents to be usedherein include all those known to those skilled in the art ofhard-surfaces cleaner compositions. In one embodiment, the compositionsherein comprise an alkoxylated glycol ether (such as n-Butoxy PropoxyPropanol (n-BPP)) or a mixture thereof.

Typically, the compositions of the present invention may comprise from0.1% to 5% by weight of the total composition, n of a solvent ormixtures thereof, alternatively from 0.5% to 5% by weight of the totalcomposition and alternatively from 1% to 3% by weight of the totalcomposition.

H. Additional Surfactant

The compositions of the present invention may comprise an additionalsurfactant, or mixtures thereof, on top of the nonionic surfactantand/or anionic surfactant already described herein. Additionalsurfactants may be desired herein as they further contribute to thecleaning performance and/or shine benefit of the compositions of thepresent invention. Surfactants to be used herein include cationicsurfactants, amphoteric surfactants, zwitterionic surfactants, andmixtures thereof.

Accordingly, the compositions of the present invention may comprise upto 15% by weight of the total composition of another surfactant or amixture thereof, on top of the nonionic surfactant already describedherein, alternatively from 0.5% to 5%, even alternatively from 0.5% to3%, and alternatively from 0.5% to 2%. Different surfactants may be usedin the present invention including anionic, cationic, zwitterionic oramphoteric surfactants. It is also possible to use mixtures of suchsurfactants without departing from the spirit of the present invention.

Suitable surfactants for use herein are zwitterionic surfactants sincethey provide excellent grease soap scum cleaning ability to thecompositions of the present invention.

Suitable zwitterionic surfactants for use herein contain both basic andacidic groups which form an inner salt giving both cationic and anionichydrophilic groups on the same molecule at a relatively wide range ofpH's. The typical cationic group is a quaternary ammonium group,although other positively charged groups like phosphonium, imidazoliumand sulfonium groups can be used. The typical anionic hydrophilic groupsare carboxylates and sulfonates, although other groups like sulfates,phosphonates, and the like can be used.

Some common examples of zwitterionic surfactants (i.e.betaine/sulphobetaine) are described in U.S. Pat. Nos. 2,082,275,2,702,279 and 2,255,082. For example Coconut dimethyl betaine iscommercially available from Seppic under the trade name of Amonyl 265®.Lauryl betaine is commercially available from Albright & Wilson underthe trade name Empigen BB/L®. A further example of betaine isLauryl-immino-dipropionate commercially available from Rhodia under thetrade name Mirataine H2C-HA®.

In one embodiment, the composition comprises sulfobetaine surfactants asthey may deliver optimum soap scum cleaning benefits. Examples ofsuitable sulfobetaine surfactants include tallow bis(hydroxyethyl)sulphobetaine, cocoamido propyl hydroxy sulphobetaines which arecommercially available from Rhodia and Witco, under the trade name ofMirataine CBS® and Rewoteric AM CAS 15® respectively.

Amphoteric and ampholytic detergents which can be either cationic oranionic depending upon the pH of the system are represented bydetergents such as dodecylbeta-alanine, N-alkyltaurines such as the oneprepared by reacting dodecylamine with sodium isethionate of theteaching of U.S. Pat. No. 2,658,072, N-higher alkylaspartic acids suchas those produced of the teaching of U.S. Pat. No. 2,438,091, and theproducts sold under the trade name “Miranol”, and described in U.S. Pat.No. 2,528,378. Additional synthetic detergents and listings of theircommercial sources can be found in McCutcheon's Detergents andEmulsifiers, North American Ed. 1980.

Suitable amphoteric surfactants include the amine oxides. Examples ofamine oxides for use herein are for instance coconut dimethyl amineoxides, C12-C16 dimethyl amine oxides. Said amine oxides may becommercially available from Clariant, Stepan, and AKZO (under the tradename Aromox®). Other suitable amphoteric surfactants for the purpose ofthe invention are the phosphine or sulfoxide surfactants.

Cationic surfactants suitable for use in compositions of the presentinvention are those having a long-chain hydrocarbyl group. Examples ofsuch cationic surfactants include the quaternary ammonium surfactantssuch as alkyldimethylammonium halogenides. Other cationic surfactantsuseful herein are also described in U.S. Pat. No. 4,228,044, Cambre,issued Oct. 14, 1980.

I. Dye

The compositions of the present invention may be colored. Accordingly,they may comprise a dye or a mixture thereof. Suitable dyes for useherein are acid-stable dyes. By “acid-stable”, it is meant herein acompound which is chemically and physically stable in the acidicenvironment of the compositions herein.

J. Malodor Control Component

The hard surface cleaning composition comprises a malodor controlcomponent. The malodor control component may include at least onevolatile aldehyde and an acid catalyst. The malodor control component isdesigned to deliver genuine malodor neutralization and not functionmerely by covering up or masking odors. A genuine malodor neutralizationprovides a sensory and analytically measurable (e.g. gas chromatograph)malodor reduction. Thus, if the malodor control component delivers agenuine malodor neutralization, the composition will reduce malodors inthe vapor and/or liquid phase.

1. Volatile Aldehydes

The malodor control component includes a mixture of volatile aldehydesthat neutralize malodors in vapor and/or liquid phase via chemicalreactions. Such volatile aldehydes are also called reactive aldehydes(RA). Volatile aldehydes may react with amine-based odors, following thepath of Schiff-base formation. Volatiles aldehydes may also react withsulfur-based odors, forming thiol acetals, hemi thiolacetals, and thiolesters in vapor and/or liquid phase. It may be desirable for these vaporand/or liquid phase volatile aldehydes to have virtually no negativeimpact on the desired perfume character of a product. Aldehydes that arepartially volatile may be considered a volatile aldehyde as used herein.

Suitable volatile aldehydes may have a vapor pressure (VP) in the rangeof about 0.0001 torr to 100 torr, alternatively about 0.0001 torr toabout 10 torr, alternatively about 0.001 torr to about 50 torr,alternatively about 0.001 torr to about 20 torr, alternatively about0.001 torr to about 0.100 torr, alternatively about 0.001 torr to 0.06torr, alternatively about 0.001 torr to 0.03 torr, alternatively about0.005 torr to about 20 torr, alternatively about 0.01 torr to about 20torr, alternatively about 0.01 torr to about 15 torr, alternativelyabout 0.01 torr to about 10 torr, alternatively about 0.05 torr to about10 torr, measured at 25° C.

The volatile aldehydes may also have a certain boiling point (B.P.) andoctanol/water partition coefficient (P). The boiling point referred toherein is measured under normal standard pressure of 760 mmHg. Theboiling points of many volatile aldehydes, at standard 760 mm Hg aregiven in, for example, “Perfume and Flavor Chemicals (Aroma Chemicals),”written and published by Steffen Arctander, 1969.

The octanol/water partition coefficient of a volatile aldehyde is theratio between its equilibrium concentrations in octanol and in water.The partition coefficients of the volatile aldehydes used in the malodorcontrol component may be more conveniently given in the form of theirlogarithm to the base 10, logP. The logP values of many volatilealdehydes have been reported. See, e.g., the Pomona92 database,available from Daylight Chemical Information Systems, Inc. (DaylightCIS), Irvine, Calif. However, the logP values are most convenientlycalculated by the “CLOGP” program, also available from Daylight CIS.This program also lists experimental logP values when they are availablein the Pomona92 database. The “calculated logP” (ClogP) is determined bythe fragment approach of Hansch and Leo (cf., A. Leo, in ComprehensiveMedicinal Chemistry, Vol. 4, C. Hansch, P. G. Sammens, J. B. Taylor andC. A. Ramsden, Eds., p. 295, Pergamon Press, 1990). The fragmentapproach is based on the chemical structure of each volatile aldehyde,and takes into account the numbers and types of atoms, the atomconnectivity, and chemical bonding. The ClogP values, which are the mostreliable and widely used estimates for this physicochemical property,are alternatively used instead of the experimental logP values in theselection of volatile aldehydes for the malodor control component.

The ClogP values may be defined by four groups and the volatilealdehydes may be selected from one or more of these groups. The firstgroup comprises volatile aldehydes that have a B.P. of about 250° C. orless and ClogP of about 3 or less. The second group comprises volatilealdehydes that have a B.P. of 250° C. or less and ClogP of 3.0 or more.The third group comprises volatile aldehydes that have a B.P. of 250° C.or more and ClogP of 3.0 or less. The fourth group comprises volatilealdehydes that have a B.P. of 250° C. or more and ClogP of 3.0 or more.The malodor control component may comprise any combination of volatilealdehydes from one or more of the ClogP groups.

In some embodiments, the malodor control component of the presentinvention may comprise, by total weight of the malodor controlcomponent, from about 0% to about 30% of volatile aldehydes from group1, alternatively about 25%; and/or about 0% to about 10% of volatilealdehydes from group 2, alternatively about 10%; and/or from about 10%to about 30% of volatile aldehydes from group 3, alternatively about30%; and/or from about 35% to about 60% of volatile aldehydes from group4, alternatively about 35%.

Exemplary volatile aldehydes which may be used in a malodor controlcomponent include, but are not limited to, Adoxal(2,6,10-Trimethyl-9-undecenal), Bourgeonal(4-t-butylbenzenepropionaldehyde), Lilestralis 33(2-methyl-4-t-butylphenyl)propanal), Cinnamic aldehyde, cinnamaldehyde(phenyl propenal, 3-phenyl-2-propenal), Citral, Geranial, Neral(dimethyloctadienal, 3,7-dimethyl-2,6-octadien-1-al), Cyclal C(2,4-dimethyl-3-cyclohexen-1-carbaldehyde), Florhydral(3-(3-Isopropyl-phenyl)-butyraldehyde), Citronellal (3,7-dimethyl6-octenal), Cymal, cyclamen aldehyde, Cyclosal, Lime aldehyde(Alpha-methyl-p-isopropyl phenyl propyl aldehyde), Methyl NonylAcetaldehyde, aldehyde C12 MNA (2-methyl-1-undecanal),Hydroxycitronellal, citronellal hydrate (7-hydroxy-3,7-dimethyloctan-1-al), Helional(alpha-methyl-3,4-(methylenedioxy)-hydrocinnamaldehyde,hydrocinnamaldehyde (3-phenylpropanal, 3-phenylpropionaldehyde),Intreleven aldehyde (undec-10-en-1-al), Ligustral, Trivertal(2,4-dimethyl-3-cyclohexene-1-carboxaldehyde), Jasmorange, satinaldehyde(2-methyl-3-tolylproionaldehyde, 4-dimethylbenzenepropanal), Lyral(4-(4-hydroxy-4-methyl pentyl)-3-cyclohexene-1-carboxaldehyde), Melonal(2,6-Dimethyl-5-Heptenal), Methoxy Melonal(6-methoxy-2,6-dimethylheptanal), methoxycinnamaldehyde(trans-4-methoxycinnamaldehyde), Myrac aldehyde isohexenylcyclohexenyl-carboxaldehyde, trifernal ((3-methyl-4-phenyl propanal,3-phenyl butanal), lilial, P.T. Bucinal, lysmeral, benzenepropanal(4-tert-butyl-alpha-methyl-hydrocinnamaldehyde), Dupical,tricyclodecylidenebutanal (4-Tricyclo5210-2,6decylidene-8butanal),Melafleur (1,2,3,4,5,6,7,8-octahydro-8,8-dimethyl-2-naphthaldehyde),Methyl Octyl Acetaldehyde, aldehyde C-11 MOA (2-methyl deca-1-al),Onicidal (2,6,10-trimethyl-5,9-undecadien-1-al), Citronellyloxyacetaldehyde, Muguet aldehyde 50(3,7-dimethyl-6-octenyl)oxyacetaldehyde), phenylacetaldehyde, Mefranal(3-methyl-5-phenyl pentanal), Triplal, Vertocitral dimethyltetrahydrobenzene aldehyde(2,4-dimethyl-3-cyclohexene-1-carboxaldehyde), 2-phenylproprionaldehyde,Hydrotropaldehyde, Canthoxal, anisylpropanal 4-methoxy-alpha-methylbenzenepropanal (2-anisylidene propanal), Cylcemone A(1,2,3,4,5,6,7,8-octahydro-8,8-dimethyl-2-naphthaldehyde), andPrecylcemone B (1-cyclohexene-1-carboxaldehyde).

Still other exemplary aldehydes include, but are not limited to,acetaldehyde (ethanal), pentanal, valeraldehyde, amylaldehyde, Scentenal(octahydro-5-methoxy-4,7-Methano-1H-indene-2-carboxaldehyde),propionaldehyde (propanal), Cyclocitral, beta-cyclocitral,(2,6,6-trimethyl-1-cyclohexene-1-acetaldehyde), Iso Cyclocitral(2,4,6-trimethyl-3-cyclohexene-1-carboxaldehyde), isobutyraldehyde,butyraldehyde, isovaleraldehyde (3-methyl butyraldehyde),methylbutyraldehyde (2-methyl butyraldehyde, 2-methyl butanal),Dihydrocitronellal (3,7-dimethyl octan-1-al), 2-Ethylbutyraldehyde,3-Methyl-2-butenal, 2-Methylpentanal, 2-Methyl Valeraldehyde, Hexenal(2-hexenal, trans-2-hexenal), Heptanal, Octanal, Nonanal, Decanal,Lauric aldehyde, Tridecanal, 2-Dodecanal, Methylthiobutanal,Glutaraldehyde, Pentanedial, Glutaric aldehyde, Heptenal, cis ortrans-Heptenal, Undecenal (2-, 10-), 2,4-octadienal, Nonenal (2-, 6-),Decenal (2-, 4-), 2,4-hexadienal, 2,4-Decadienal, 2,6-Nonadienal,Octenal, 2,6-dimethyl 5-heptenal, 2-isopropyl-5-methyl-2-hexenal,Trifernal, beta methyl Benzenepropanal,2,6,6-Trimethyl-1-cyclohexene-1-acetaldehyde, phenyl Butenal (2-phenyl2-butenal), 2.Methyl-3(p-isopropylphenyl)-propionaldehyde,3-(p-isopropylphenyl)-propionaldehyde, p-Tolylacetaldehyde(4-methylphenylacetaldehyde), Anisaldehyde (p-methoxybenzene aldehyde),Benzaldehyde, Vernaldehyde(1-Methyl-4-(4-methylpentyl)-3-cyclohexenecarbaldehyde), Heliotropin(piperonal) 3,4-Methylene dioxy benzaldehyde, alpha-Amylcinnamicaldehyde, 2-pentyl-3-phenylpropenoic aldehyde, Vanillin (4-methoxy3-hydroxy benzaldehyde), Ethyl vanillin (3-ethoxy4-hydroxybenzaldehyde), Hexyl Cinnamic aldehyde, Jasmonal H(alpha-n-hexyl-cinnamaldehyde), Floralozone,(para-ethyl-alpha,alpha-dimethyl Hydrocinnamaldehyde), Acalea(p-methyl-alpha-pentylcinnamaldehyde), methylcinnamaldehyde,alpha-Methylcinnamaldehyde (2-methyl 3-pheny propenal),alpha-hexylcinnamaldehyde (2-hexyl 3-phenyl propenal), Salicylaldehyde(2-hydroxy benzaldehyde), 4-ethyl benzaldehyde, Cuminaldehyde(4-isopropyl benzaldehyde), Ethoxybenzaldehyde,2,4-dimethylbenzaldehyde, Veratraldehyde (3,4-dimethoxybenzaldehyde),Syringaldehyde (3,5-dimethoxy 4-hydroxybenzaldehyde), Catechaldehyde(3,4-dihydroxybenzaldehyde), Safranal (2,6,6-trimethyl-1,3-dienemethanal), Myrtenal (pin-2-ene-1-carbaldehyde), Perillaldehyde L-4(1-methylethenyl)-1-cyclohexene-1-carboxaldehyde),2,4-Dimethyl-3-cyclohexene carboxaldehyde, 2-Methyl-2-pentenal,2-methylpentenal, pyruvaldehyde, formyl Tricyclodecan, Mandarinaldehyde, Cyclemax, Pino acetaldehyde, Corps Iris, Maceal, and Corps4322.

In one embodiment, the malodor control component includes a mixture oftwo or more volatile aldehydes selected from the group consisting of2-ethoxy Benzylaldehyde, 2-isopropyl-5-methyl-2-hexenal, 5-methylFurfural, 5-methyl-thiophene-carboxaldehyde, Adoxal, p-anisaldehyde,Benzylaldehyde, Bourgenal, Cinnamic aldehyde, Cymal, Decyl aldehyde,Floral super, Florhydral, Helional, Lauric aldehyde, Ligustral, Lyral,Melonal, o-anisaldehyde, Pino acetaldehyde, P.T. Bucinal, Thiophenecarboxaldehyde, trans-4-Decenal, trans trans 2,4-Nonadienal, Undecylaldehyde, and mixtures thereof.

In some embodiments, the malodor control component includes fastreacting volatile aldehydes. “Fast reacting volatile aldehydes” refersto volatile aldehydes that either (1) reduce amine odors by 20% or morein less than 40 seconds; or (2) reduce thiol odors by 20% or more inless than 30 minutes.

In one embodiment, the malodor control component includes a mixture ofthe volatile aldehydes listed in Table 1 and referred to herein asAccord A.

TABLE 1 Accord A ClogP VP (torr) Material Wt. % CAS Number Group @25° C.Intreleven Aldehyde 5.000 112-45-8 3 0.060 Florhydral 10.000 125109-85-54 0.008 Floral Super 25.000 71077-31-1 3 0.030 Scentenal 10.00086803-90-9 2 0.010 Cymal 25.000 103-95-7 4 0.007 o-anisaldehyde 25.000135-02-4 1 0.032

In another embodiment, the malodor control component includes a mixtureof the volatile aldehydes listed in Table 2 and referred to herein asAccord B.

TABLE 2 Accord B ClogP VP (torr) Material Wt. % CAS Number Group @25° C.Intreleven Aldehyde 2.000 112-45-8 3 0.060 Florhydral 20.000 125109-85-54 0.008 Floral Super 10.000 71077-31-1 3 0.030 Scentenal 5.00086803-90-9 2 0.010 Cymal 25.000 103-95-7 4 0.007 Floralozone 10.00067634-14-4 4 0.005 Adoxal 1.000 141-13-9 4 0.007 Methyl Nonyl 1.000110-41-8 3 0.030 Acetaldehyde Melonal 1.000 106-72-9 3 0.670o-anisaldehyde 25.000 135-02-4 1 0.032

In another embodiment, the malodor control component includes a mixtureof about 71.2% volatile aldehydes, the remainder being other an esterand an alcohol perfume raw material. This mixture is listed in Table 3and referred to herein as Accord C.

TABLE 3 Accord C ClogP VP (torr) Material Wt. % CAS Number Group @25° C.Intreleven Aldehyde 2.000 112-45-8 3 0.060 Florhydral 10.000 125109-85-54 0.008 Floral Super 5.000 71077-31-1 3 0.030 Scentenal 2.000 86803-90-92 0.010 Cymal 15.000 103-95-7 4 0.007 Floralozone 12.000 67634-14-4 40.005 Adoxal 1.000 141-13-9 4 0.007 Methyl Nonyl 1.000 110-41-8 3 0.030Acetaldehyde Melonal 1.000 106-72-9 3 0.670 Flor Acetate 11.8005413-60-5 1 0.060 Frutene 7.000 17511-60-3 4 0.020 Helional 5.0001205-17-0 2 0.0005 Bourgeonal 2.000 18127-01-0 4 0.004 Linalool 10.00078-70-6 3 0.050 Benzaldehyde 0.200 100-52-7 1 1.110 o-anisaldehyde15.000 135-02-4 1 0.320

Accords A, B, or C can be formulated in with other perfume raw materialsin an amount, for example, of about 10% by weight of the malodor controlcomponent. Additionally, the individual volatile aldehydes or a variouscombination of the volatile aldehydes can be formulated into a malodorcontrol component. In certain embodiments, the volatile aldehydes may bepresent in an amount up to 100%, by weight of the malodor controlcomponent, alternatively from 1% to about 100%, alternatively from about2% to about 100%, alternatively from about 3% to about 100%,alternatively about 50% to about 100%, alternatively about 70% to about100%, alternatively about 80% to about 100%, alternatively from about 1%to about 20%, alternatively from about 1% to about 10%, alternativelyfrom about 1% to about 5%, alternatively from about 1% to about 3%,alternatively from about 2% to about 20%, alternatively from about 3% toabout 20%, alternatively from about 4% to about 20%, alternatively fromabout 5% to about 20%, by weight of the composition.

In some embodiments where volatility is not important for neutralizing amalodor, the present invention may include poly-aldehydes, for example,di-, tri-, tetra-aldehydes. Such embodiments may include laundrydetergents, additive, and the like for leave-on, through the wash, andrinse-off type of applications.

2. Acid Catalyst

The malodor control component of the present invention may include aneffective amount of an acid catalyst to neutralize sulfur-basedmalodors. It has been found that certain mild acids have an impact onaldehyde reactivity with thiols in the liquid and vapor phase. It hasbeen found that the reaction between thiol and aldehyde is a catalyticreaction that follows the mechanism of hemiacetal and acetal formationpath. When the present malodor control component contains an acidcatalyst and contacts a sulfur-based malodor, the volatile aldehydereacts with thiol. This reaction may form a thiol acetal compound, thus,neutralizing the sulfur-based odor. Without an acid catalyst, onlyhemi-thiol acetal is formed.

Suitable acid catalysts have a VP, as reported by Scifinder, in therange of about 0.001 torr to about 38 torr, measured at 25° C.,alternatively about 0.001 torr to about 14 torr, alternatively fromabout 0.001 to about 1, alternatively from about 0.001 to about 0.020,alternatively about 0.005 to about 0.020, alternatively about 0.010 toabout 0.020.

The acid catalyst may be a weak acid. A weak acid is characterized by anacid dissociation constant, K_(a), which is an equilibrium constant forthe dissociation of a weak acid; the pKa being equal to minus thedecimal logarithm of K_(a). The acid catalyst may have a pKa from about4.0 to about 6.0, alternatively from about 4.3 and 5.7, alternativelyfrom about 4.5 to about 5, alternatively from about 4.7 to about 4.9.Suitable acid catalyst include those listed in Table 4.

TABLE 4 VP (torr) @ Material 25° C. Formic Acid 36.5 Acetic Acid 13.9Trimethyl Acetic Acid 0.907 Phenol (alkaline in liquid apps yet 0.610acidic in vapor phase) Tiglic acid 0.152 Caprylic acid 0.0222 5-Methylthiophene carboxylic acid 0.019 Succinic acid 0.0165 Benzoic acid 0.014Mesitylenic acid 0.00211

Depending on the desired use of the malodor control component, one mayconsider the scent character or the affect on the scent of the malodorcontrol component when selecting an acid catalyst. In some embodimentsof the malodor control component, it may be desirable to select an acidcatalyst that provides a neutral to pleasant scent. Such acid catalystsmay have a VP of about 0.001 torr to about 0.020 torr, measured at 25°C., alternatively about 0.005 torr to about 0.020 torr, alternativelyabout 0.010 torr to about 0.020 torr Non-limiting examples of such acidcatalyst include 5-methyl thiophene carboxaldehyde with carboxylic acidimpurity, succinic acid, or benzoic acid.

The malodor control component may include about 0.05% to about 5%,alternatively about 0.1% to about 1.0%, alternatively about 0.1% toabout 0.5%, alternatively about 0.1% to about 0.4%, alternatively about0.4% to about 1.5%, alternatively about 0.4% of an acid catalyst byweight of the malodor control component.

In an acetic acid system, the present malodor control component mayinclude about 0.4% of acetic acid (50:50 TC:DPM, 0.4% acetic acid).

TABLE 5 Actual % acetic % Butanethiol Sample Formulated acid in DPMreduction @ 30 min. 50:50 TC:DPM 0% Acetic Acid 0.00 12.00 50:50 TC:DPM0.05% Acetic Acid 0.04 14.65 50:50 TC:DPM 0.1% Acetic Acid 0.10 25.6650:50 TC:DPM 0.2% Acetic Acid 0.42 34.68 50:50 TC:DPM 0.5% Acetic Acid1.00 24.79 50:50 TC:DPM 1.0% Acetic Acid 2.00 7.26

When an acid catalyst is present with a volatile aldehyde (or RA), theacid catalyst may increase the efficacy of the volatile aldehyde onmalodors in comparison to the malodor efficacy of the volatile aldehydeon its own. For example, 1% volatile aldehyde and 1.5% benzoic acidprovides malodor removal benefit equal to or better than 5% volatilealdehyde alone.

The malodor control component may have a pH from about 3 to about 8,alternatively from about 4 to about 7, alternatively from about,alternatively from about 4 to about 6.

3. Optional Ingredients

The malodor control component may, optionally, include odor maskingagents, odor blocking agents, and/or diluents. For example, the malodorcontrol component may include a mixture of volatile aldehydes forneutralizing a malodor, perfume ionones, and a diluent. Alternatively,the malodor control component may include 100% volatile aldehydes.

“Odor-masking agents” refer to known compounds (e.g. perfume rawmaterials) that mask or hide a malodorous compound. Odor-masking mayinclude a compound with a non-offensive or pleasant smell that is dosedsuch it limits the ability to sense a malodorous compound. Odor-maskingmay involve the selection of compounds which coordinate with ananticipated malodor to change the perception of the overall scentprovided by the combination of odorous compounds.

“Odor blocking agents” refer to known compounds that dull the humansense of smell.

Exemplary diluents include dipropylene glycol methyl ether, and3-methoxy-3-methyl-1-butanol, and mixtures thereof.

The malodor control component may also, optionally, include perfume rawmaterials that solely provide a hedonic benefit (i.e. that do notneutralize malodors yet provide a pleasant fragrance). Suitable perfumesare disclosed in U.S. Pat. No. 6,248,135, which is incorporated in itsentirety by reference.

II. Method of Cleaning a Hard-Surface or an Object

The present invention further encompasses a method of cleaning a hardsurface or an object, alternatively removing limescale from saidhard-surface or said object.

The method of the present invention comprises the steps of: applying aliquid acidic hard surface cleaning composition comprising formic acid,citric acid and an alkaline material, and having a pH of above 2.0; andmixtures thereof, onto said hard-surface or said object; leaving saidcomposition on said hard-surface or said object to act; optionallywiping said hard-surface or object and/or providing mechanicalagitation, and then rinsing said hard-surface or said object.

By “hard-surface”, it is meant herein any kind of surfaces typicallyfound in and around houses like bathrooms, kitchens, basements andgarages, e.g., floors, walls, tiles, windows, sinks, showers, showerplastified curtains, wash basins, WCs, dishes, fixtures and fittings andthe like made of different materials like ceramic, enamel, painted andun-painted concrete, plaster, bricks, vinyl, no-wax vinyl, linoleum,melamine, Formica®, glass, any plastics, metals, chromed surface and thelike. The term surfaces as used herein also include household appliancesincluding, but not limited to, washing machines, automatic dryers,refrigerators, freezers, ovens, microwave ovens, dishwashers and so on.Some hard surfaces cleaned with the liquid aqueous acidic hard surfacecleaning composition herein are those located in a bathroom, in a toiletor in a kitchen, basements, garages as well as outdoor such as gardenfurniture, gardening equipments, driveways etc.

The objects herein are objects that are subjected to limescale formationthereon. Such objects may be water-taps or parts thereof, water-valves,metal objects, objects made of stainless-steel, cutlery and the like.

One method of cleaning a hard-surface or an object (alternativelyremoving limescale from said hard-surface or said object) comprises thestep of applying a composition of the present invention onto saidhard-surface or object, leaving said composition on said hard-surface orobject to act, alternatively for an effective amount of time,alternatively for a period comprised between 1 and 10 minutes,alternatively for a period comprised between 2 and 4 minutes; optionallywiping said hard-surface or object with an appropriate instrument, e.g.a sponge; and then alternatively rinsing said surface with water.

Even though said hard-surface or object may optionally be wiped and/oragitated during the process herein, it has been surprisingly found thatthe process of the present invention allows good limescale removalperformance without any additional mechanical wiping and/or agitationaction. The lack of need for additional wiping and/or mechanical;agitation provides an added convenience for the user of the compositionsherein.

In another execution of the present invention is provided a method ofcleaning an object, alternatively removing limescale from an object,comprising the step of immersing said object in a bath comprising acomposition of the present invention, leaving said object in said bathfor the composition to act, alternatively for an effective amount oftime, alternatively for a period comprised between 1 and 10 minutes,alternatively for a period comprised between 2 and 4 minutes; and thenalternatively rinsing said object with water.

The compositions of the present invention may be contacted to thesurface or the object to be treated in its neat form or in its dilutedform. Alternatively, the composition is applied in its neat form.

By “diluted form”, it is meant herein that said composition is dilutedby the user, typically with water. The composition is diluted prior useto a typical dilution level of 10 to 400 times its weight of water,alternatively from 10 to 200 and alternatively from 10 to 100. Usualrecommended dilution level is a 1.2% dilution of the composition inwater.

The compositions of the present invention are particularly suitable fortreating hard-surfaces located in and around the house, such as inbathrooms, toilets, garages, on driveways, basements, gardens, kitchens,etc., and alternatively in bathrooms. It is however known that suchsurfaces (especially bathroom surfaces) may be soiled by the so-called“limescale-containing soils”. By “limescale-containing soils” it ismeant herein any soil which contains not only limescale mineraldeposits, such as calcium and/or magnesium carbonate, but also soap scum(e.g., calcium stearate) and other grease (e.g. body grease). By“limescale deposits” it is mean herein any pure limescale soil, i.e.,any soil or stains composed essentially of mineral deposits, such ascalcium and/or magnesium carbonate.

The compositions herein may be packaged in any suitable container, suchas bottles, alternatively plastic bottles, optionally equipped with anelectrical or manual trigger spray-head.

EXAMPLES

The examples herein are meant to exemplify the present invention but arenot necessarily used to limit or otherwise define the scope of thepresent invention. All numerical values in the below examples are weight%, by total weight of the composition unless otherwise stated.

Examples: I II III IV V VI VII VIII IX Acids Formic acid 3.0 1.5 2.5 2.01.8 2.5 3.0 1.0 3.0 Citric acid 1.5 6.0 4.5 4.0 7.0 2.0 1.0 4.0 2.0Alkaline Material: NaOH - to pH: 2.1 2.4 2.2 3.8 3.0 KOH - to pH: 2.42.9 2.2 2.8 Water up to 100% Examples: X XI XII XIII XIV XV XVI XVIIXVIII Acids Formic acid 2.0 2.7 2.5 1.8 1.5 2.0 2.8 1.8 4.0 Acetic acid— — 0.75 — 0.5 — — — — Citric acid 3.5 4.6 4.0 8.0 1.5 3.0 2.0 — —Lactic acid — — — 1.0 — 2.0 1.0 — 1.5 Sulfuric acid — — — — — — — 3.03.0 Surfactants Neodol 91-8 ® 0.5 2.2 2.2 2.2 2.5 0.45 2.5 — — SulphatedSafol 2.0 — — — — — — — — 23 ® H-LAS — — — — — 0.80 — 0.90 1.30 NaCS — —— — — 1.80 — 2.20 2.50 Polymers: Kelzan T ® 0.40 0.25 0.25 0.25 0.300.10 0.40 0.45 0.60 PVP 0.25 0.05 — 0.25 0.05 — 0.25 — — SF 1288 ® — — —— — 0.60 0.90 1.80 Solvent: n-BPP 1.0 — — 1.5 — — — — — Misc.: BHT 0.030.03 0.03 0.03 0.05 — 0.03 0.15 0.15 Malodor Control 0.05 0.50 0.20 0.500.30 0.50 0.25 0.40 0.35 Component Dye 0.01 0.005 0.005 0.01 0.01 0.010.01 0.01 0.005 Alkaline Material: KOH - to pH: 2.3 — — — 2.8 — — — —NaOH - to pH: — 2.2 2.3 3.6 — 2.5 2.3 — — pH (w/o alkaline — — — — — — —0.5 0.5 material added) Water: up to 100% Examples: XIX XX XXI XXIIXXIII Acids Formic acid 2.5 2.8 2.7 1.0 2.0 Citric acid 3.6 1.0 2.0 3.01.0 Oxalic acid 1.0 — — — — Surfactants Neodol 91-8 ® 2.5 0.5 2.2 1.52.0 Sulphated Safol — — — — 0.8 23 ® Sodium Lauryl — 3.0 2.0 1.5 —Sulphate Kelzan T ® 0.28 0.10 0.35 0.25 0.40 PVP 0.05 — 0.25 0.05 0.25n-BPP — 3.5 2.5 1.6 2.5 BHT 0.04 — — — — Malodor Control 0.25 0.60 0.400.20 0.35 Component Dye 0.005 0.005 0.01 0.005 0.01 KOH - to pH: — 3.6 —— — NaOH - to pH: 2.3 — 3.0 3.3 3.6 pH (w/o alkaline — — — — materialadded) Water: up to 100% Formic acid, citric acid, lactic acid, aceticacid, oxalic acid and sulphuric acid are commercially available fromAldrich. Neodol 91-8 ® is a C₉-C₁₁ EO8 nonionic surfactant, commerciallyavailable from SHELL. Sulphated Safol 23 ® is a branched C₁₂₋₁₃ sulphatesurfactant based on Safol 23 ®, an alcohol commercially available fromSasol, which has been sulphated. Sodium lauryl sulfate is a linearC12-14 sulfate which is commercially available from Aldrich. n-BPP isn-butoxy propoxy propanol. Kelzan T ® is a Xanthan gum supplied byKelco. PVP is a vinylpyrrolidone homopolymer, commercially availablefrom ISP Corporation. SF 1288 ® is a silicone-polyether copolymer,commercially available from Momentive Performance Materials. BHT isButylated Hydroxy TolueneAnalytical Test—Effect of Volatile Aldehydes on Amine-Based andSulfur-Based Malodors

Malodor standards are prepared by pipeting 1 mL of butylamine(amine-based malodor) and butanethiol (sulfur-based malodor) into a 1.2liter gas sampling bag. The bag is then filled to volume with nitrogenand allowed to sit for at least 12 hours to equilibrate.

A 1 μL sample of each volatile aldehyde listed in Table 6 and of eachAccord (A, B, and C) listed in Tables 1 to 3 is pipeted into individual10 mL silanized headspace vials. The vials are sealed and allowed toequilibrate for at least 12 hours. Repeat 4 times for each sample (2 forbutylamine analysis and 2 for butanethiol analysis).

After the equilibration period, 1.5 mL of the target malodor standard isinjected into each 10 mL vial. For thiol analysis, the vials containinga sample +malodor standard are held at room temperature for 30 minutes.Then, a 1 mL headspace syringe is then used to inject 250 μL of eachsample/malodor into a GC/MS split/splitless inlet. For amine analysis, a1 mL headspace syringe is used to inject 500 μL of each sample/malodorimmediately into the GC/MS split/splitless inlet. A GC pillow is usedfor the amine analysis to shorten the run times.

Samples are then analyzed using a GC/MS with a DB-5, 20 m, 1 μm filmthickness column with an MPS-2 autosampler equipment with staticheadspace function. Data is analyzed by ion extraction on each total ioncurrent (56 for thiol and 30 for amine) and the area is used tocalculate the percent reduction from the malodor standard for eachsample.

Table 6 shows the effect of certain volatile aldehydes on neutralizingamine-based and sulfur based malodors at 40 seconds and 30 minutes,respectively.

TABLE 6 At least 20% butylamine At least 20% reduction at butanethiolPerfume Raw Material (R—CHO) 40 secs.? reduction at 30 mins.? 2,4,5Trimethoxy Benzaldehyde No No 2,4,6-Trimethoxy-benzylaldehyde No No2-ethoxy benzylaldehyde Yes Yes 2-isopropyl-5-methyl-2-hexenal Yes Yes2-methyl-3-(2-furyl)-propenal No No 3,4,5 Trimethoxy Benzaldehyde No No3,4-Trimethoxy-benzylaldehyde No No 4-tertbutyl benzylaldehyde Yes No5-methyl furfural Yes Yes 5-methyl-thiophene- No Yes carboxaldehydeAdoxal Yes No Amyl cinnamic aldehyde No No Benzylaldehyde Yes NoBourgenal No Yes Cinnamic aldehyde Yes Yes Citronelyl Oxyacetaldehyde NoNo Cymal Yes No Decyl aldehyde Yes No Floral Super Yes Yes FlorhydralYes Yes Floralozone No No Helional Yes No Hydroxycitronellal No NoLauric aldehyde Yes No Ligustral Yes No Lyral Yes No Melonal Yes NoMethyl nonyl acetaldehyde No No o-anisaldehyde Yes Yes p-anisaldehydeYes No Pino acetaldehyde Yes Yes P.T. Bucinal Yes No ThiopheneCarboxaldehyde Yes No Trans-4-decenal Yes Yes Trans Trans 2,4-NonadienalYes No Undecyl aldehyde Yes No

Table 7 shows the percent reduction of butylamine and butaniethiol at 40seconds and 30 minutes, respectively, for Accords A, B, and C.

TABLE 7 % reduction of butylamine at % reduction of butanethiol atAccord 40 secs. 30 mins. Accord A 76.58 25.22 Accord B 51.54 35.38Accord C 65.34 24.98Analytical Test—Effect of Acid Catalysts on Sulfur-Based Malodors

The above analytical test is repeated using samples containing an acidcatalyst to test their effect on sulfur-based malodors. Specifically, a1 μL aliquot of each of the following controls and acid catalyst samplesare pipeted into individual 10 mL silanized headspace vials induplicate: thiophene carboxyaldehyde as a control; a 50/50 mixture ofthiophene carboxaldehyde and each of the following acid catalysts at0.04%, 0.10%, 0.43% in DPM, 1.02% in DPM, and 2.04% in DPM: phenol,mesitylenic acid, caprylic acid, succinic acid, pivalic acid, tiglicacid, and benzoic acid.

FIG. 1 demonstrates that low vapor pressure acid catalysts provide up to3 times better reduction of sulfur-based malodors in comparison to thecontrol.

Analytical Test—Effect of Volatile Aldehydes and Acid Catalyst onAmine-Based and Sulfur-Based Malodors

The above analytical test is repeated using sample formulationscontaining volatile aldehydes (or RA) and an acid catalyst, as outlinedin Tables 8 and 9.

Tables 8 and 9 show that a perfume mixture having as little as 1%volatile aldehyde along with 1.5% acid catalyst performs better atreducing butylamine and butanethiol than the same perfume mixture having5% volatile aldehyde.

TABLE 8 % butylamine % butanethiol reduction at reduction Formulation 40secs. at 30 mins. Perfume Mixture w/ 5% RA 34.21 — 2.40 — (Control)Perfume Mixture w/ 1% RA and 41.63 +7.42 11.95 +9.55 w/ 1.5% BenzoicAcid Perfume Mixture w/ 3% RA and 36.19 +1.98 13.56 +11.16 w/ 1.5%Benzoic Acid Perfume A Mixture w/ 5% RA and 41.26 +7.05 9.56 +5.02 w/1.5% Benzoic Acid

TABLE 9 % butylamine % butanethiol Reduction at reduction at Formulation40 secs. 30 mins. Perfume mixture w/ 5% RA 4.94 — 10.52 — (Control)Perfume mixture w/ 1% RA and 11.61 +6.67 18.82 +8.30 w/ 1.5% BenzoicAcid Perfume mixture w/ 3% RA and 26.89 +21.95 14.85 +4.33 w/ 1.5%Benzoic Acid Perfume mixture w/ 5% RA and 20.27 +15.33 16.84 +6.32 w/1.5% Benzoic Acid

The dimensions and values disclosed herein are not to be understood asbeing strictly limited to the exact numerical values recited. Instead,unless otherwise specified, each such dimension is intended to mean boththe recited value and a functionally equivalent range surrounding thatvalue. For example, a dimension disclosed as “40 mm” is intended to mean“about 40 mm”

Every document cited herein, including any cross referenced or relatedpatent or application, is hereby incorporated herein by reference in itsentirety unless expressly excluded or otherwise limited. The citation ofany document is not an admission that it is prior art with respect toany invention disclosed or claimed herein or that it alone, or in anycombination with any other reference or references, teaches, suggests,or discloses any such invention. Further, to the extent that any meaningor definition of a term in this document conflicts with any meaning ordefinition of the same term in a document incorporated by reference, themeaning or definition assigned to that term in this document shallgovern.

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is, therefore,intended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

What is claimed:
 1. A hard surface cleaning composition comprising: (a)an acidic component; (b) a surfactant selected from the group consistingof nonionic surfactants, anionic surfactants, cationic surfactants;amphoteric surfactants, zwitterionic surfactants, and mixtures thereof;and (c) a surface modifying polymer; (d) a malodor control componentcomprising an effective amount of: (i) at least one volatile aldehyde;and (ii) 5-methyl thiophene carboxylic acid; and (e) an aqueous carrier.2. The composition of claim 1 wherein said at least one volatilealdehyde is selected from the group consisting of 2-ethoxybenzylaldehyde, 2-isopropyl-5-methyl-2-hexenal, 5-methyl furfural,cinnamic aldehyde, floral super, florhydral, o-anisaldehyde, pinoacetaldehyde, trans-4-decenal, and mixtures thereof.
 3. The compositionof claim 1 wherein said at least one volatile aldehyde comprise florsuper and o-anisaldehyde.
 4. The composition of claim 1 wherein said atleast one volatile aldehyde have a vapor pressure from about 0.001 torrto about 0.100 torr.
 5. The composition of claim 1 wherein said at leastone volatile aldehyde comprise about 25% of group 1 volatile aldehydes,by weight of said malodor control component.
 6. The composition of claim1 wherein said at least one volatile aldehyde comprise about 10% ofgroup 2 volatile aldehydes, by weight of said malodor control component.7. The composition of claim 1 wherein said at least one volatilealdehyde comprise from about 10% to about 30% of group 3 volatilealdehydes, by weight of said malodor control component.
 8. Thecomposition of claim 1 wherein said at least one volatile aldehydecomprise from about 35% to about 60% of group 4 volatile aldehydes, byweight of said malodor control component.
 9. The composition of claim 1wherein said at least one volatile aldehyde is selected from the groupconsisting of: Accord A, Accord B, Accord C, and mixtures thereof. 10.The composition of claim 1 wherein said at least one volatile aldehydecomprise about 1% to about 10% of Accord A, by weight of said malodorcontrol component.
 11. The composition of claim 1 wherein saidcomposition has a pH of above about
 2. 12. The composition of claim 1wherein said at least one volatile aldehyde comprise three or morevolatile aldehydes having a VP of about 0.001 torr to about 0.100 torr.13. The composition of claim 1 wherein said at least one volatilealdehyde are present in an amount from about 0.015% to about 1%, byweight of said hard surface cleaning composition.
 14. The composition ofclaim 1 wherein said acidic component is about 0.01% to about 5%, byweight of the total composition, of formic acid.
 15. The composition ofclaim 1, wherein said acidic component is from about 0.1 to about 12%,by weight of the total composition, of citric acid.
 16. The compositionof claim 1, wherein said acidic component comprises formic acid andcitric acid.
 17. The composition of claim 1, wherein said surfactant isa nonionic surfactant which is the condensation product of ethyleneand/or propylene oxide with an alcohol having a straight alkyl chaincomprising from about 6 to about 22 carbon atoms, wherein the degree ofethoxylation/propoxylation is from about 1 to about
 15. 18. Thecomposition of claim 1, wherein said surfactant is an alkyl sulphateanionic surfactant.
 19. The composition of claim 1, wherein saidsurfactant is a mixture of a nonionic surfactant and an anionicsurfactant.
 20. The composition of claim 1, wherein said surfacemodifying polymer is selected from the group consisting of:vinylpyrrolidone homopolymer or copolymer; polysaccharide polymer; andmixtures thereof.
 21. The composition of claim 1 further comprising amaterial selected from the group consisting of: solvents, radicalscavengers, caustics, perfumes, dyes, and mixtures thereof.
 22. Thecomposition of claim 1, wherein said composition further comprises analkaline material selected from the group consisting of: sodiumhydroxide, potassium hydroxide, lithium hydroxide, alkali metal,monoethanolamine, triethanolamine, ammonia, ammonium carbonate, cholinebase, and mixtures thereof.
 23. The composition of claim 1, wherein saidcomposition further comprises and alkaline material selected from thegroup consisting of: sodium hydroxide, potassium hydroxide, and mixturesthereof.
 24. The composition of claim 1, wherein said compositionfurther comprises uncomplexed cyclodextrin.
 25. The composition of claim1 wherein said composition further comprises a water-soluble metallicsalt selected from the group consisting of: zinc salts, copper salts,and mixtures thereof.
 26. A method of cleaning a hard surface or anobject, comprising the steps of: (a) applying the hard surface cleaningcomposition of claim 1 onto said hard-surface or said object; (b)leaving said composition on said hard-surface or said object to act;optionally, wiping said hard-surface or object; and (c) rinsing saidhard-surface or said object.